Application Note Oil & Gas

BTU Analysis Using a Gas Chromatograph

Since the early eighties, it has become common in the United States, Typical ranges are as follows:
and elsewhere in the world, for natural gas to be bought and sold
Component Range
based on the amount of energy delivered. The quantity of energy
C6+ Hexanes and heavier (0–0.7 %)
delivered is calculated by multiplying the gas volume per unit time
C3 Propane (0–5 %)
by the heating value (BTU) per unit volume.
IC4 Isobutane (0–1 %)
NC4 Normal Butane (0–1 %)
Gas chromatography is normally employed for the calculation of
NeoC5 Neopentane (0–1 %)
the heating value. However, when the gas chromatograph runs
IC5 Isopentane (0–1 %)
an analysis we not only get the heating value, but other valuable
NC5 Normal Pentane (0–1 %)
information, such as gas composition and relative density. This
N2 Nitrogen (0–15 %)
additional information is used in the gas volume calculations.
NC5 Normal Pentane (0–1 %)
Gas chromatographs (GCs) have been widely used in hydrocarbon
N2 Nitrogen (0–15 %)
processing facilities when high-quality product specifications are
C1 Methane (0–100 %)
required, or when rigid custody transfer standards are needed for
CO2 Carbon Dioxide (0–15 %)
natural gas trading.
C2 Ethane (0–15 %)

Gas chromatography is a scientific method in which a gas sample

is separated into its component parts for measurement. The gas
chromatograph consists of subsystems that inject the sample,
separate the sample, detect the components, integrate the peaks,
and report the results. The injection, separation, and detection all
occur in the heart of the GC known as the GC oven. The integration
and calculation of results are done in the controller which can be
considered the brains of the system.
This paper describes the basics of how a BTU analyzer works. In
a typical natural gas application the gas is separated into eleven
different components. Hexanes and heavier components such
as heptane, octane, and nonane are combined together to form
a single peak known as C6+. Because we separate up to these
components, we call this a C6+ application.
Gas Chromatograph Oven for C6+
Natural Gas Applications
The gas chromatograph oven is heated at a constant temperature
(around 80 °C), and has a constant flow of carrier gas (usually
high-purity helium) flowing through it. The carrier gas is used for
transporting the sample through the oven during the separation
process. The oven consists of three valves and four columns, and a
set of balanced thermal conductivity detectors.
The first valve is the sample valve which is used for injecting the
sample into the system. The second valve is called a backflush valve.
The backflush valve is used for backing out the C6+ heavies so that
they can be detected first without having to go through columns
two and three. The third valve is a dual-column valve which is used
to trap the light components and allow the medium components
to go around column three. Of the four columns, the first three are
made up of tubing with special material inside called packing that
is designed to separate the gas into its different components. The
fourth column acts as a buffer to keep the flow steady when the
valves are switched. The following steps illustrate the process taking
place in the GC oven.
Oil & Gas
Step 1 - Start of an analysis. Sample valve (V-1) OFF, backflush valve
(V-2) ON, and dual column valve (V-3) ON. The sample purging system
maintains a sample in the gaseous phase and passes the sample through
transport tubing to the sample valve and through the sample loop.
Step 2 - The sample valve is turned ON to capture a precise volume of
sample, and to allow the carrier gas (helium) to sweep the sample into
column 1 to start the analysis.
Step 3 - The sample valve turns back OFF to start purging the next
stream. The backflush valve turns OFF, reversing the flow through
column 1 so that C6 and heavier components elute first (all combined as
a single peak). Note: By switching the direction of flow through column
1, we bypass columns 2 and 3. This helps to expedite the analysis.
Page 2
Step 4 - C6+ (heavy) is on its way to the detector. Column 2 separates
the mediums — C3, C4s and C5s — while the lightest components — N2,
C1, CO2, and C2 — continue traveling through column 2 into column 3
Step 5 - Dual column turns OFF after trapping the lightest components,
N2, C1, CO2, and C2. The medium components bypass column 3 by going
through the restrictor column and following C6+ to the detector. Once
again, this helps speed up the analysis.
Step 6 - After the heavy and medium components elute to the detector,
the dual-column valve is turned back on, freeing the light components
and allowing them to cross the detector next.
This ends the analysis and the next one is ready to begin. Typical
analysis time is four minutes.
 Oil & Gas

Qualitative and Quantitative Information Figure 1 - Chromatogram

In a gas chromatograph, it is vital that three things never change.
1. Oven temperature
2. Flow of carrier gas
3. Sample size

By keeping these three things constant, we are able to run

continuous analysis that repeat within ± .5 BTU / 1000 BTUs
(± .25 BTU / 1000 BTU’s when installed in a temperature controlled
environment. By knowing this time (retention time), we can
program the controller and have it identify the peaks as they come
out. This identifying of the peaks is known as qualitative information.

To find out quantitative information, we use a set of matched

thermal conductivity detectors (TCDs) integrated in a bridge circuit.
One detector is the reference and is only exposed to the carrier gas.
RF = Raw Area / Calibration Concentration
The other is called the measure detector and is exposed to both
RF = 100 / 5 = 20
the carrier and the separated sample components. When carrier
gas is flowing across both the reference and measure detectors
Given: Sample stream gas is run, and the raw area calculated by
at the same time, the detector bridge is balanced and no signal is
the controller is 200. What is the quantity of ethane in the sample
generated. When a component other than carrier gas is going across
stream?
the measure detector, the bridge is not balanced and a signal is
generated, amplified, and sent to the controller. This raw signal is Mole % of Sample = Raw Area / RF
integrated by the controller which then calculates a raw area. A raw Mole % ethane = 200 / 20 = 10 %
area is calculated for each peak (see Figure 1).
Note: Realistically the raw area for the different components will
Raw areas are calculated by integrating the area under each typically be in the thousands.
peak. Each raw area is directly proportional to the component
concentration During a calibration, raw areas are divided by the BTU Calculations from Mole Percent
known calibration concentrations and response factors (RF) are After the controller has calculated the mole percent of each
calculated. Each response factor is only changed during a calibration. component, it normalizes the components so that the summation
The following formula shows how a response factor is used for of all mole percentages equal one hundred. A simplified example
calculating the mole percent of a sample stream component. of normalization using only four components instead of eleven is as
follows:
Response Factor = Raw Area / Calibration Concentration Mole
% of component = Raw Area / Response Factor Measured Component Normalized Component
N2 0.99 % 1.0 %
C1 89.1 % 90 %
The following is a simplified example of how the response factor is
CO2 0.99 % 1.0 %
calculated and then used in the stream analysis.
C2 7.92 % 8.0 %
Total 99 % 100 %
Given: Calibration was run, and a raw area for ethane calculated by
the controller is 100. To normalize mole %:
CONCNn = (CONCn / CONCt) X 100
Given: The calibration gas had a molecular concentration of 5 % Where:
ethane in the bottle (this was programmed into the controller). CONCNn = Normalized concentration of component n
CONCn = Measured concentration of component n
CONCt = Measured total concentration of components

Page 3
Figure 2 - Analysis Report Glossary:
1. Carrier Gas - the gas supply, regulated to a specific pressure
which carries the sample through the columns to the detector.
The most common carrier gas used for natural gas applications is
pure helium.
2. Columns - various tubes or capillaires mounted in a
chromatograph oven that are packed with solid material,
combinations of liquid and solid material, or liquid material.
3. Analytical valves are installed in the chromatograph oven both
to inject a sample for analysis and to divert it or its separated
components as per the application schedule (timed events).
4. Detectors are devices or assemblies of instruments that transmit
electronic signals proportional to the concentration of a
component. The thermal conductivity detector (TCD) is the most
widely used detector for natural gas analysis.
5. A calibration cylinder is used as the basis of comparison for each
The analysis report gives the BTU values, as well as gas composition and of the components measured on a stream(s). The components
relative density which can be used for volumetric calculations.
and ranges blended in the cylinder are roughly comparable to
the stream.
After the mole percentages have been normalized, the controller
6. Retention time - the amount of time elapsed from the start of
multiplies each of these percentages by a corresponding BTU value
an analysis to the maximum moment of influence a component
often taken from an internal table (GPA 2145). From the individual
makes on the detector.
BTU, calculations for each component the controller can then do a
7. The chromatogram is the graphic depiction of the
summation and calculate a total BTU per cubic foot of gas. This is an
chromatograph analysis. It is used to allow the technician to view
uncorrected or ideal BTU value. To get a corrected or real BTU value,
the baseline integrity and peak separation as a part of quality
the controller multiplies the ideal BTU by the compressibility factor.
assurance.
Figure 2 shows the results from an analysis report.
8. The molecular percentage (mole %) is the volumetric
measurement of the percentage of a component in a sample
(also known as the percentage by volume).
9. Response factor - used for then quantitative measurement.
RF = RA/CC
Where: RF = Response Factor, RA = Raw Area, CC = Calibration
Concentration from calibration gas.

EmersonProcess.com/GasAnalysis

YouTube.com/user/RosemountAnalytical Analyticexpert.com

Twitter.com/Rosemount_News Facebook.com/Rosemount

©2015 Emerson Process Management. All rights reserved.

The Emerson logo is a trademark and service mark of Emerson Electric Co. All other marks are the
property of their respective owners.
Emerson Process Management
10241 West Little York, Suite 200 The contents of this publication are presented for information purposes only, and while effort has
Houston, Texas 77040
been made to ensure their accuracy, they are not to be construed as warranties or guarantees,
USA
Toll Free + 866 422 3683 express or implied, regarding the products or services described herein or their use or
T + 713 396 8880 applicability. All sales are governed by our terms and conditions, which are available on request.
F + 713 466 8175 We reserve the right to modify or improve the designs or specifications of our products at any
GC.CSC@Emerson.com time without notice.

NGC-ANO-OilGas-BTU-Analysis-Using-Gas-Chromatograph